JP2004331697A - Pressure-sensitive adhesive and optical member using the same - Google Patents
Pressure-sensitive adhesive and optical member using the same Download PDFInfo
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- JP2004331697A JP2004331697A JP2003125145A JP2003125145A JP2004331697A JP 2004331697 A JP2004331697 A JP 2004331697A JP 2003125145 A JP2003125145 A JP 2003125145A JP 2003125145 A JP2003125145 A JP 2003125145A JP 2004331697 A JP2004331697 A JP 2004331697A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polarising Elements (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【0001】
【発明が属する技術分野】
本発明は、液晶表示装置の液晶セル等の光学部品に、偏光板や位相差板等の光学部材を貼付するために用いられる粘着剤、およびそれを用いた光学部材に関する。
【0002】
【従来の技術】
液晶表示装置の液晶セル等の光学部品には、偏光板や偏光板と位相差板の積層体が貼付される。偏光板は、一般的にはポリビニルアルコール系偏光子の両面をトリアセチルセルロース系保護フィルムで挟んだ多層構造を有し、この偏光板の片面または両面のトリアセチルセルロース系保護フィルム上に、粘着剤層が形成されている。偏光板は、この粘着剤層を介して液晶セル等の光学部品に貼付され液晶表示装置として使用される。近年、液晶表示装置は、パーソナルコンピューターのディスプレイ、液晶テレビをはじめとする屋内用途から、カーナビゲーション用ディスプレイ等の車両搭載用途等にも広く使用され、その使用環境が非常に苛酷になりつつある。
【0003】
液晶表示装置に使用されている偏光板は、その材料特性から寸法安定性が乏しく、熱あるいは湿熱条件下で伸縮して寸法が大きく変化するため、このような条件下では粘着剤層の発泡や偏光板の液晶セルからの浮きハガレなどの問題が生じやすくなる。
これらの問題を解消する粘着剤として、アルキル基の炭素数が1〜12の(メタ)アクリル酸のアルキルエステルを主成分とするアクリル系ポリマーからなる感圧性接着剤であって、該感圧性接着剤が重量平均分子量10万以下のポリマー成分を15重量%以下含有し、かつ重量平均分子量100万以上のポリマー成分を10重量%以上含有するアクリル系ポリマーからなる感圧性接着剤が知られている(例えば、特許文献1参照。)。
【0004】
前記感圧性接着剤を用いることにより、粘着剤層の発泡や偏光板の液晶セルからの浮きハガレは抑制できるが、偏光板の寸法変化による応力を吸収・緩和することができず、偏光板の周縁部に応力が集中するため、液晶表示装置の周縁部と中央部の明るさが異なり、液晶表示装置表面に色むら・白ぬけが発生する問題があった。
この液晶表示装置表面の色むら・白ぬけを解消する粘着剤として、重量平均分子量が100万以上である高分子量(メタ)アクリル系共重合体100重量部と、重量平均分子量が3万以下の低分子量(メタ)アクリル系共重合体20〜200重量部と、多官能性化合物0.005〜5重量部からなる偏光板用粘着剤が知られている(例えば、特許文献2参照。)。
【0005】
また、反応性官能基を含有する重量平均分子量100万〜250万の高分子量アクリル系ポリマーとガラス転移点が0℃〜−80℃の重量平均分子量3万〜10万の低分子量アクリル系ポリマーと架橋構造が形成可能な官能基を有する多官能性化合物からなる偏光フィルム用粘着組成物が知られている(例えば、特許文献3参照。)。
【特許文献1】
特開平1−66283号公報
【特許文献2】
特開平10−279907号公報
【特許文献3】
特開2002−121521号公報
【0006】
【発明が解決しようとする課題】
特許文献2には、該文献に開示されている偏光板粘着剤は、偏光板の寸法変化に追随できるため、液晶素子に色むら・白ぬけが発生しにくいと記載されている。しかし、特許文献2に開示されている偏光板粘着剤は、多官能性化合物と三次元架橋した高分子量(メタ)アクリル系共重合体中に、架橋しにくいか若しくは架橋しない低分子量(メタ)アクリル系(共)重合体を存在させることで応力緩和性を発現させており、色むら・白ヌケの改良は可能であるが、低分子量(メタ)アクリル系重合体がブリードしやすく、被着体が汚染される課題が残されている。
【0007】
また、特許文献3には、該文献に開示されている偏光フィルム用粘着組成物は、色むら・白ぬけが発生しにくい性能と低分子量アクリル系ポリマーがブリードし難い性能を併せ持つと記載されているが、より過酷な環境下での液晶表示装置の使用において、性能バランスを発揮させることが難しい。
そこで、本発明の目的は、熱あるいは湿熱条件下でも粘着剤層の発泡や偏光板のハガレ等が発生せず、偏光板の伸縮等により生じる応力集中を緩和して液晶表示装置に色むら・白ぬけ現象を発生させず、更には偏光板の張りなおし時に問題となる被着体汚染やヘイズを低減できる粘着剤を提供することにある。
【0008】
【課題を解決するための手段】
本発明における粘着剤は、高分子量の共重合体(A)と、該共重合体(A)の存在下でカルボキシル基を有する単量体とその他の単量体をラジカル共重合して得られる低分子量の共重合体(B)と、多官能性化合物(C)とを特定の比率で含むことにより、偏光板の寸法変化によって生ずる色むら・白ヌケ現象を緩和する性質と、熱あるいは湿熱条件下でも発泡やハガレ等が抑制できる性質を併せ持つものである。
【0009】
すなわち、本発明における粘着剤は、下記単量体(a)および(b)をラジカル共重合してなる重量平均分子量100万以上200万以下の共重合体(A)と、該共重合体(A)100重量部に対して、上記共重合体(A)の存在下で下記単量体(c)および(d)をラジカル共重合してなる重量平均分子量1万以上10万以下の共重合体(B)20〜100重量部、および上記共重合体(A)および/または上記共重合体(B)と反応可能な反応性官能基を少なくとも2個有する多官能性化合物(C)0.003〜3重量部からなる粘着剤である。
(a) 反応性官能基およびエチレン性不飽和二重結合を有する単量体
(b) (a)と共重合可能な他のエチレン性不飽和二重結合を有する単量体
(c) カルボキシル基およびエチレン性不飽和二重結合を有する単量体
(d)(c)と共重合可能な他のエチレン性不飽和二重結合を有する単量体
上記粘着剤において、共重合体(A)を構成する単量体(a)の共重合比率は0.1〜15重量%であることが好ましく、単量体(b)の共重合比率は85〜99.9重量%であることが好ましい。
【0010】
また、本発明における粘着剤の製造方法は、下記の工程(1)〜(3)を有する粘着剤の製造方法である。
(1)反応性官能基およびエチレン性不飽和二重結合を有する単量体(a)および(a)と共重合可能な他のエチレン性不飽和二重結合を有する単量体(b)を転化率50%〜90%でラジカル共重合して共重合体(A)を重合する工程。
(2)共重合体(A)の重合時に残留する単量体とカルボキシル基およびエチレン性不飽和二重結合を有する単量体(c)を共重合体(A)の存在下でラジカル共重合して共重合体(B)を重合する工程。
(3)共重合体(A)および/または共重合体(B)と反応可能な反応性官能基を少なくとも2個有する多官能性化合物(C)を添加する工程。
【0011】
上記の工程(2)において、共重合体(A)の重合時に残留する単量体とカルボキシル基およびエチレン性不飽和二重結合を有する単量体(c)を転化率70%〜100%でラジカル共重合して共重合体(B)を重合することが好ましい。
また、本発明における粘着剤は、上記の方法で製造される粘着剤である。
また、本発明における光学部材は、上記のいずれかの粘着剤からなる粘着剤層が、光学部材の少なくとも一方の面に形成されていることを特徴とする光学部材である。
【0012】
【発明の実施の形態】
まず、本発明の粘着剤について説明する。
粘着剤に含まれる重合体(A)は、反応性官能基およびエチレン性不飽和二重結合を有する単量体(a)と、(a)と共重合可能な他のエチレン性不飽和二重結合を有する単量体(b)をラジカル共重合して得られる共重合体である。反応性官能基としては、カルボキシル基、水酸基、アミノ基、アミド基、マレイミド基、イタコンイミド基、スクシンイミド基、エポキシ基等があげられる。また、単量体(a)および単量体(b)しては、(メタ)アクリル系単量体、ビニル系単量体が好適に用いられる。
【0013】
カルボキシル基を有する単量体(a)の具体例としては、(メタ)アクリル酸、β−カルボキシエチルアクリレート、イタコン酸、クロトン酸、フマル酸、無水フマル酸、マレイン酸、無水マレイン酸、マレイン酸ブチル等があげられる。水酸基を有する単量体(a)の具体例としては、2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、4−ヒドロキシブチル(メタ)アクリレート、6−ヒドロキシヘキシル(メタ)アクリレート、8−ヒドロキシオクチル(メタ)アクリレート、10−ヒドロキシデシル(メタ)アクリレート、12−ヒドロキシラウリル(メタ)アクリレート、(4−ヒドロキシメチルヘキシル)−メチルアクリレート、クロロ−2−ヒドロキシプロピル(メタ)アクリレート、ジエチレングリコールモノ(メタ)アクリレート、カプロラクトン変性(メタ)アクリレート類、ポリエチレングリコール(メタ)アクリレート類、ポリプロピレングリコール(メタ)アクリレート類等が挙げられる。
【0014】
アミノ基を有する単量体(a)の具体例としては、アミノメチル(メタ)、ジメチルアミノメチル(メタ)アクリレート、ジメチルアミノエチル(メタ)アクリレート、ジメチルアミノプロピル(メタ)アクリレート等が挙げられる。
アミド基を有する単量体(a)の具体例としては、(メタ)アクリルアミド、N−アクリロイルモルホリン、N−置換(メタ)アクリルアミド、N−ビニルピロリドン等が挙げられる。
マレイミド基を有する単量体(a)の具体例としては、N−シクロヘキシルマレイミド、N−イソプロピルマレイミド、N−ラウリルマレイミド、N−フェニルマレイミド等が挙げられる。
イタコンイミド基を有する単量体(a)の具体例としては、N−メチルイタコンイミド、N−エチルイタコンイミド、N−ブチルイタコンイミド、N−オクチルイタコンイミド、N−2−エチルヘキシルイタコンイミド、N−シクロヘキシルイタコンイミド、N−ラウリルイタコンイミド等が挙げられる。
【0015】
スクシンイミド基を有する単量体(a)の具体例としては、N−(メタ)アクリロイルオキシメチレンスクシンイミド、N−(メタ)アクリロイル−6−オキシヘキサメチレンスクシンイミド、N−(メタ)アクリロイル−8−オキシオクタメチレンスクシンイミド等が挙げられる。
エポキシ基を有する単量体(a)の具体例としては、グリシジル(メタ)アクリレート等が挙げられる。
これらの単量体は、単独であるいは複数組み合わせて使用することができる。
共重合体(A)を構成する単量体(a)の共重合比率は、単量体の全量を基準として0.1〜15重量%であることが好ましい。その共重合比率が0.1重量%より少ない場合には、粘着剤の凝集力が低下し、加熱環境下で粘着剤の発泡や浮きハガレが起こることがある。また、15重量%より多い場合には、粘着剤の粘着力が低下したり、偏光板の伸縮に起因する応力集中を十分に吸収・緩和する性質が発現しにくい。
【0016】
また、単量体(b)の具体例としては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、n−ブチル(メタ)アクリレート、iso−ブチル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、n−オクチル(メタ)アクリレート、iso−オクチル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、iso−ノニル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ベンジル(メタ)アクリレート、メトキシエチル(メタ)アクリレート、エトキシエチル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート等が挙げられる。また、スチレン、メチルスチレン、ビニルトルエン等の芳香族ビニルモノマー、酢酸ビニル、(メタ)アクリロニトリル等も挙げられる。
【0017】
共重合体(A)を構成する単量体(b)の共重合比率は、単量体の全量を基準として85〜99.9重量%であることが好ましい。その共重合比率が85重量%より少ない場合には、偏光板や光学部品への密着性が低下する。また、99.9重量%より多い場合には、反応性官能基有する単量体(a)の含有量が少なくなり、粘着剤の凝集力が低下し、加熱環境下で粘着剤の発泡や浮きハガレが起こることがある。
【0018】
共重合体(A)は、公知の任意の方法で製造することができる。
例えば、共重合体(A)は、単量体の合計100重量部に対して、0.001〜1重量部の重合開始剤を用いて、塊状重合、溶液重合などの方法、好ましくは溶液重合法により合成される。重合開始剤としては、アゾ系化合物、有機過酸化物が用いられ、重合開始剤は2種類以上を併用しても良い。また、溶液重合の場合、重合溶媒としては、酢酸エチル、酢酸n−ブチル、酢酸イソブチル、トルエン、アセトン、ヘキサン、メチルエチルケトン等が用いられる。重合溶媒は2種類以上混合して用いても良い。
【0019】
重合開始剤のうちアゾ系化合物としては、例えば、2,2’−アゾビスイソブチロニトリル、2,2’−アゾビス(2−メチルブチロニトリル)、1,1’−アゾビス(シクロヘキサン1−カルボニトリル)、2,2’−アゾビス(2,4−ジメチルバレロニトリル)、2,2’−アゾビス(2,4−ジメチル−4−メトキシバレロニトリル)、ジメチル2,2’−アゾビス(2−メチルプロピオネート)、4,4’−アゾビス(4−シアノバレリック酸)、2,2’−アゾビス(2−ヒドロキシメチルプロピオニトリル)、2,2’−アゾビス[2−(2−イミダゾリン−2−イル)プロパン]等が挙げられる。
【0020】
また、有機過酸化物としては、例えば、過酸化ベンゾイル、t−ブチルパーベンゾエイト、クメンヒドロパーオキシド、ジイソプロピルパーオキシジカーボネート、ジ−n−プロピルパーオキシジカーボネート、ジ(2−エトキシエチル)パーオキシジカーボネート、t−ブチルパーオキシネオデカノエート、t−ブチルパーオキシビバレート、(3,5,5−トリメチルヘキサノイル)パーオキシド、ジプロピオニルパーオキシド、ジアセチルパーオキシド等があげられる。
【0021】
共重合体(A)の重量平均分子量は、100万以上200万以下であることが必要であり、更に120万以上180万以下であることが好ましい。重量平均分子量が100万よりも小さい共重合体(A)は、架橋して使用しても粘着剤の凝集力が不足して、発泡や浮きハガレが生じる。また、重量平均分子量が200万より大きいと、粘着剤の粘度が高くなり塗工等の作業性が劣る。なお、共重合体(A)の重量平均分子量は、共重合体(B)の重合を開始する前に反応溶液の一部をサンプリングして、ゲルパーミエーションクロマトグラフィー(GPC)測定を実施して算出する。
【0022】
粘着剤に含まれる共重合体(B)は、上記共重合体(A)の存在下でカルボキシル基およびエチレン性不飽和二重結合を有する単量体(c)および(c)と共重合可能な他のエチレン性不飽和二重結合を有する単量体(d)をラジカル共重合してなる重量平均分子量1万以上10万以下の共重合体である。共重合体(A)の存在下で単量体(c)および単量体(d)をラジカル共重合してなる共重合体(A)よりも低分子量の共重合体(B)が粘着剤中に含まれると、熱あるいは湿熱条件下でも粘着剤の発泡やハガレ等が発生せず、偏光板の伸縮等により生じる応力集中を緩和して液晶素子に色むら・白ぬけ現象を発生させない。
【0023】
単量体(c)および単量体(d)としては、(メタ)アクリル系単量体、ビニル系単量体が好適に用いられる。単量体(c)の具体例としては、(メタ)アクリル酸、β−カルボキシエチルアクリレート、イタコン酸、クロトン酸、フマル酸、無水フマル酸、マレイン酸、無水マレイン酸、マレイン酸ブチル等が挙げられる。これらの単量体は、単独であるいは複数組み合わせて使用することができる。
共重合体(B)を構成する単量体(c)の共重合比率は、単量体(c)と単量体(d)との合計量を基準として0.1〜50重量%であることが好ましく、0.5〜30重量%であることがより好ましい。
【0024】
単量体(d)としては、共重合体(A)を構成する単量体(a)のうち、カルボキシル基以外の反応性官能基を有する単量体(a)、および単量体(b)を使用することができる。
共重合体(B)は、共重合体(A)の存在下で、カルボキシル基およびエチレン性不飽和二重結合を有する単量体(c)および(c)と共重合可能な他のエチレン性不飽和二重結合を有する単量体(d)とを、共重合体(A)と同様な方法でラジカル共重合することにより製造することができる。共重合体(B)は、単量体(a)と単量体(b)を転化率50〜90%でラジカル共重合して共重合体(A)を重合した後に、残留する単量体と単量体(c)を共重合体(A)の存在下でラジカル共重合して製造することが好ましい。
【0025】
また、共重合体(A)の重合時に残留する単量体と単量体(c)とは、転化率70〜100%でラジカル共重合することが好ましい。ここで転化率とは、単量体を重合して得られる共重合体の重量を、原料として用いた単量体の総重量で除した値である。
上記の転化率で共重合体(A)および共重合体(B)を重合することにより、共重合体(A)100重量部に対して共重合体(B)を20〜100重量部の範囲に収めることが容易となる。
【0026】
共重合体(B)は、溶液重合法で合成することが好ましく、重合体(A)合成時の5〜50重量倍程度の重合開始剤、すなわち単量体の合計100重量部に対して、0.005〜50重量部の重合開始剤を使用することが好ましい。また、共重合体(B)の合成時には、ラウリルメルカプタン、n−ドデシルメルカプタン等のメルカプタン類、α−メチルスチレンダイマー、リモネン等の連鎖移動剤を使用しても良い。
【0027】
共重合体(B)の重量平均分子量は、1万以上10万以下であることが必要であり、更に2万以上5万以下であることが好ましい。重量平均分子量が1万より小さい共重合体(B)を用いる場合には、凝集力が不足して発泡や浮きハガレが生じやすい。また、重量平均分子量が10万を超える共重合体(B)を用いる場合には、偏光板の伸縮に起因する応力集中を十分に吸収・緩和する性質が発現しにくい。ここで共重合体(B)の重量平均分子量は、共重合体(A)と共重合体(B)の混合物をGPC測定し、得られたGPCスペクトルと前述の方法で測定した共重合体(A)のGPCスペクトルとの差スペクトルから算出する。
【0028】
粘着剤に含まれる共重合体(B)の含有量は、共重合体(A)100重量部に対して20〜100重量部であり、好ましくは20〜50重量部である。共重合体(B)の含有量が20重量部より少ない場合には、偏光板の伸縮に起因する応力集中を十分に吸収・緩和する性質が発現しにくい。また、共重合体(B)の含有量が100重量部を超える場合には、粘着剤の凝集力が不足して発泡や浮きハガレが生じやすい。
【0029】
共重合体(A)と共重合体(B)の重量比は、以下の方法で求められる。すなわち、まず、重合体(B)の重合を開始する前にサンプリングした溶液の一定量を重量既知の容器に入れて精秤し、この精秤した溶液を加熱乾燥して、共重合体以外の成分を揮散させ、共重合体(A)のみが残った容器を精秤し、一定量の溶液に含まれる共重合体(A)の重量を算出する。次に共重合体(B)の重合完了後に、共重合体(A)と共重合体(B)が含まれる溶液をサンプリングし、共重合体(A)の重量を算出したときと同様の方法で、一定量の溶液に含まれる共重合体(A)と共重合体(B)の重量を算出する。そして一定量の溶液に含まれる共重合体(A)および共重合体(A)と共重合体(B)の混合物の重量を、同量の溶液に含まれる共重合体(A)および共重合体(A)と共重合体(B)の混合物の重量に換算し、共重合体(A)と共重合体(B)の混合物の重量から共重合体(A)を差し引くことにより、共重合体(B)の重量を算出する。
【0030】
粘着剤に含まれる共重合体(A)および/または共重合体(B)と反応可能な反応性官能基を少なくとも2個有する多官能性化合物(C)は、共重合体(A)が有する反応性官能基および/または共重合体(B)が有するカルボキシル基やカルボキシル基以外の反応性官能基と反応可能な反応性官能基を少なくとも2個、好ましくは2〜4個有する化合物である。このような多官能性化合物の例としては、イソシアネート系化合物、エポキシ系化合物、アミン系化合物、金属キレート系化合物、アジリジン系化合物などが挙げられる。特に、イソシアネート系化合物、エポキシ系化合物、アジリジン系化合物が好ましい。多官能性化合物は、単独であるいは複数組み合わせて使用することができる。
【0031】
イソシアネート系化合物の例としては、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート、水添キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、水添ジフェニルメタンジイソシアネート、テトラメチルキシリレンジイソシアネート、ナフタレンジイソシアネート、トリフェニルメタントリイソシアネート、ポリメチレンポリフェニルイソシアネートなどのポリイソシアネート化合物、およびこれらポリイソシアネート化合物とトリメチロールプロパン等のポリオール化合物とのアダクト体、これらポリイソシアネート化合物のビュレット体やイソシアヌレート体、更にはこれらポリイソシアネート化合物と公知のポリエーテルポリオールやポリエステルポリオール、アクリルポリオール、ポリブタジエンポリオール、ポリイソプレンポリオール等とのアダクト体等が挙げられる。
【0032】
また、エポキシ系化合物の例としては、ビスフェノールA−エピクロロヒドリン型のエポキシ系樹脂、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、1,6−ヘキサンジオールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ジグリシジルアニリン、N,N,N’,N’−テトラグリシジル−m−キシリレンジアミン、1、3−ビス(N、N‘−ジグリシジルアミノメチル)シクロヘキサン、N,N,N’,N’−テトラグリシジルアミノフェニルメタン、トリグルシジル等が挙げられる。
【0033】
また、アジリジン化合物の例としては、N,N‘−ジフェニルメタン−4,4’−ビス(1−アジリジンカルボキサイト)、N,N‘−トルエン−2,4−ビス(1−アジリジンカルボキサイト)、ビスイソフタロイル−1−(2−メチルアジリジン)、トリ−1−アジリジニルホスフィンオキサイド、N,N‘−ヘキサメチレン−1,6−ビス(1−アジリジンカルボキサイト)、トリメチロールプロパントリ−β−アジリジニルプロピオネート、テトラメチロールメタントリ−β−アジリジニルプロピオネート、トリス−2,4,6−(1−アジリジニル)−1、3、5−トリアジン等が挙げられる。
【0034】
多官能性化合物(C)の含有量は、上記共重合体(A)100重量部に対して、0.003〜3重量部である。多官能化合物(C)の含有量が0.003重量部未満では、着色剤の凝集力が不足して、発泡や浮きハガレが生じやすい。また、3重量部より多い場合には、偏光板の伸縮に起因する応力集中を十分に吸収・緩和する性質が発現しにくい。
【0035】
粘着剤には、シランカップリング剤を配合することが好ましい。シランカップリング剤としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルメチルメトキシシランN−(2−アミノエチル)3−アミノプロピルトリメトキシシラン、N−(2−アミノエチル)3−アミノプロピルメチルジメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、メルカプトブチルトリメトキシシランγ−メルカプトプロピルメチルジメトキシシラン等が挙げられる。
【0036】
粘着剤中のシランカップリング剤の含有量は共重合体(A)100重量部に対して、0.01〜2重量部が好ましい。0.01重量部より少ないと、その物性の改善効果が乏しく、2重量部を越えると、粘着剤が高価になるのみならず、浮きハガレの原因となる。
また、粘着剤には、紫外線吸収剤、酸化防止剤、粘着付与樹脂、可塑剤、消泡剤、レベリング調整剤を配合しても良い。
【0037】
粘着剤は、下記の工程(1)〜(3)を経ることにより製造することができる。
(1)反応性官能基およびエチレン性不飽和二重結合を有する単量体(a)および(a)と共重合可能な他のエチレン性不飽和二重結合を有する単量体(b)を転化率50〜90%でラジカル共重合して共重合体(A)を重合する工程。
(2)共重合体(A)の重合時に残留する単量体とカルボキシル基およびエチレン性不飽和二重結合を有する単量体(c)を共重合体(A)の存在下、転化率70%〜100%でラジカル共重合して共重合体(B)を重合する工程。
(3)共重合体(A)および/または共重合体(B)と反応可能な反応性官能基を少なくとも2個有する多官能性化合物(C)を添加する工程。
【0038】
次に、本発明の光学部材について説明する。
本発明の光学部材は、本発明の粘着剤からなる粘着剤層が、光学部材の少なくとも一方の面に形成されている光学部材である。
粘着剤層を形成する光学部材としては、偏光フィルム、位相差フィルム、楕円偏光フィルム、反射防止フィルム、輝度向上フィルムが挙げられる。
【0039】
粘着剤層の形成は、通常使用されている塗布装置を用いて行うことができる。塗布装置としては、例えば、ロールナイフコーター、ダイコーター、ロールコーター、バーコーター、グラビアロールコーター、リバースロールコーター、ディッピング、ブレードコーターなどがあげられる。
また、粘着剤層の乾燥膜厚は、偏光板の伸縮に起因する応力集中を吸収、緩和するのに適切な膜厚と経済性を考慮して、5〜100μmであることが好ましい。
【0040】
【実施例】
次に、実施例を示して本発明を更に詳細に説明するが、本発明はこれらによって限定されるものではない。尚、以下の説明において、部および%とあるのは、重量部および重量%をそれぞれ意味するものとする。
(合成例1)
攪拌機、温度計、還流冷却器、滴下装置、窒素導入管を備えた反応容器に、n−ブチルアクリレート99.0部、4−ヒドロキシブチルアクリレート1.0部、アセトン150.0部、2,2’−アゾビスイソブチロニトリル0.06部を仕込み、この反応容器内の空気を窒素ガスで置換した後、攪拌しながら窒素雰囲気下中で、この反応溶液を60℃に昇温させ、5時間反応させた。反応終了後、トルエンを190部とアクリル酸0.25部および2,2’−アゾビス(2,4−ジメチルバレロニトリル)0.50部を添加して、70℃に昇温し、6時間反応させた。反応後、トルエン55部を添加して室温まで冷却し、固形分20.0%の重合体溶液Aを得た。
【0041】
(合成例2〜9)
表1に示すように、反応性官能基およびエチレン性不飽和二重結合を有する単量体(a)、(a)と共重合可能な他のエチレン性不飽和二重結合を有する単量体(b)、カルボキシル基およびエチレン性不飽和二重結合を有する単量体(c)の種類および量を変える以外は、合成例1と同様にして、重合体溶液B〜Iを得た。
【0042】
(合成例10)
合成例1と同様な反応装置に、ブチルアクリレート99.0部、4−ヒドロキシブチルアクリレート1.0部、酢酸エチル163.0部、2,2’−アゾビスイソブチロニトリル0.06部を仕込み、この反応容器内の空気を窒素ガスで置換した後、攪拌しながら窒素雰囲気下中で、この反応溶液を80℃に昇温させ、4時間反応させた。反応終了後、トルエンを176部とアクリル酸0.25部および2,2’−アゾビス(2,4−ジメチルバレロニトリル)0.50部を添加して、75℃に昇温し、6時間反応させた。反応後、トルエン57部を添加して室温まで冷却し、固形分20.0%の重合体溶液Jを得た。
【0043】
(合成例11)
合成例1と同様な反応装置に、ブチルアクリレート60.0部、2−エチルヘキシルアクリレート37.0部、4−ヒドロキシブチルアクリレート3.0部、アセトン150.0部、2,2’−アゾビスイソブチロニトリル0.06部を仕込み、この反応容器内の空気を窒素ガスで置換した後、攪拌しながら窒素雰囲気下中で、この反応溶液を60℃に昇温させ、5時間反応させた。反応終了後、酢酸エチルを65.0部とアクリル酸0.28部および2,2’−アゾビスイソブチロニトリル0.06部を添加して、60℃に昇温し、8時間反応させた。反応後、トルエン183部を添加して室温まで冷却し、固形分20.0%の重合体溶液Kを得た。
【0044】
(合成例12)
合成例1と同様な反応装置に、ブチルアクリレート99.0部、4−ヒドロキシブチルアクリレート1.0部、アセトン150.0部、2,2’−アゾビスイソブチロニトリル0.06部を仕込み、この反応容器内の空気を窒素ガスで置換した後、攪拌しながら窒素雰囲気下中で、この反応溶液を60℃に昇温させ、3時間反応させた。反応終了後、トルエンを1.1部とアクリル酸0.55部および2,2’−アゾビス(2,4−ジメチルバレロニトリル)1.1部を添加して、70℃に昇温し、7時間反応させた。反応後、トルエン236部を添加して室温まで冷却し、固形分20.0%の重合体溶液Lを得た。
【0045】
(合成例13)
合成例1と同様な反応装置に、ブチルアクリレート99.0部、4−ヒドロキシブチルアクリレート1.0部、アセトン150.0部、2,2’−アゾビスイソブチロニトリル0.06部を仕込み、この反応容器内の空気を窒素ガスで置換した後、攪拌しながら窒素雰囲気下中で、この反応溶液を60℃に昇温させ、10時間反応させた。反応終了後、トルエンを198部とアクリル酸0.08部および2,2’−アゾビス(2,4−ジメチルバレロニトリル)0.16部を添加して、70℃に昇温し、6時間反応させた。反応後、トルエン51部を添加して室温まで冷却し、固形分20.0%の重合体溶液Mを得た。
【0046】
(合成例14)
合成例1と同様な反応容器に、n−ブチルアクリレート99.0部、4−ヒドロキシブチルアクリレート1.0部、アセトン150.0部、2,2’−アゾビスイソブチロニトリル0.06部を仕込み、この反応容器内の空気を窒素ガスで置換した後、攪拌しながら窒素雰囲気下中で、この反応溶液を60℃に昇温させ、5時間反応させた。反応後、トルエン150部を添加して室温まで冷却し、固形分20.0%の重合体溶液Nを得た。重合体の重量平均分子量は161万、Mw/Mnは4.8であった。
【0047】
(合成例15)
合成例1と同様な反応容器に、n−ブチルアクリレート99.0部、4−ヒドロキシブチルアクリレート1.0部、トルエン150.0部、α−メチルスチレンダイマー1部および2,2’−アゾビスイソブチロニトリル2部を仕込み、この反応容器内の空気を窒素ガスで置換した後、撹拌しながら窒素雰囲気下で、この反応溶液を70℃に昇温させ、6時間反応させた。反応後、トルエン150部を添加して室温まで冷却し、固形分40.0%の重合体溶液Oを得た。重合体の重量平均分子量は2.4万、Mw/Mnは2.8であった。
【0048】
合成例1〜13で得られた重合体溶液について、共重合体(A)の重量平均分子量(Mw)、共重合体(A)合成時の転化率、共重合体(B)の重量平均分子量(Mw)、共重合体(B)合成時の転化率、および共重合体(A)100部に対する共重合体(B)の比率を先に説明した方法で算出した。結果を表1に示す。
【0049】
【表1】
【0050】
表1中の単量体の略号を以下に示す。
4−HBA:4−ヒドロキシブチルアクリレート
AA:アクリル酸
HEA:2−ヒドロキシエチルアクリレート
HEMA:2−ヒドロキシエチルメタクリレート
BA:ブチルアクリレート
2EHA:2−エチルヘキシルアクリレート
LA:ラウリルアクリレート
EA:エチルアクリレート
VAc:酢酸ビニル
【0051】
なお、共重合体の重量平均分子量は、GPC測定で求めたポリスチレン換算の重量平均分子量であり、GPC測定条件は以下のとおりである。
装置:Shodex GPC System−21(昭和電工(株)製)
カラム:Shodex KF−602.5を1本、Shodex KF−606Mを2本(昭和電工(株)製)の合計3本を連結して使用。
溶媒:テトラヒドロフラン
流速:0.5ml/min
温度:40℃
試料濃度:0.1wt%
試料注入量:50μl
【0052】
(実施例1)
合成例1で得られた重合体溶液A 100重量部に対して、XDI/TMP(キシリレンジイソシネートのトリメチローププロパンアダクト体)0.05部およびシランカップリング剤(信越化学工業(株)製「KBM403」)0.1部を添加してよく撹拌して粘着剤を得た。この粘着剤を剥離処理されたポリエステルフィルムに塗工して乾燥させ、25μmの粘着剤層を設けた後に、それを偏光フィルムの片面に転写して偏光フィルムを粘着加工した。この粘着加工された偏光フィルムを温度23℃相対湿度50%の条件で1週間熟成させて偏光板を得た。
【0053】
(実施例2〜7および比較例1〜7)
表2に示す種類および量の重合体溶液、多官能性化合物(C)、およびシランカップリング剤を用いた以外は、実施例1と全く同様にして粘着剤を製造し、得られた粘着剤を用いて粘着加工した偏光板を作成した。
(比較例8)
重合体溶液Aの代わりに、重合体溶液N:100部と重合体溶液O:30部を混合した重合体溶液を用いた以外は、実施例1と全く同様にして粘着剤を製造し、得られた粘着剤を用いて粘着加工した偏光板を作成した。
【0054】
【表2】
【0055】
表2中の多官能性化合物およびシランカップリング剤の略号を以下に示す。
TAT:トリス−2,4,6−(1−アジリジニル)−1、3、5−トリアジンTGMXDA:N,N,N’,N’−テトラグリシジル−m−キシリレンジアミン
KBM903:信越化学工業(株)製シランカップリング剤「KBM903」
KBM803:信越化学工業(株)製シランカップリング剤「KBM803」
KBM9007:信越化学工業(株)製シランカップリング剤「KBM9007」
【0056】
実施例および比較例で得られた粘着剤、および粘着加工した偏光板について、耐熱性能、耐湿熱性能、光学特性およびリワーク性を以下の方法で評価した。結果を表3に示す。
(1)耐熱性能、耐湿熱性能、光学特性(白ぬけ)の評価方法
粘着加工した偏光板を150mm×80mmの大きさにカットし、厚さ1.1mmのフロートガラス板の両面に、偏光板の吸収軸が直交するようにラミネーターを用いて貼り付けた。続いて、この偏光板を貼り付けたガラス板を50℃5気圧の条件のオートクレーブ内に20分保持させてガラス板に密着させた。更に、この偏光板とガラス板の構成物を80℃で500時間放置した後の浮きハガレ(耐熱性能)、60℃、相対湿度90%で500時間放置した後の浮きハガレ(耐湿熱性)、およびこの60℃相対湿度90%で500時間放置した後の偏光板とガラス板の構成物に光を透過させたときの光漏れ(白ぬけ)を目視で観察し、三段階で評価した。
◎は「浮きハガレ・白ぬけが全く認められない」、○は「若干浮きハガレ・白ぬけが認められるが、実用上問題がない」、△は「明らかに浮きハガレ・白ぬけが認められ、実用上問題がある」をそれぞれ意味する。
【0057】
(2)リワーク性の評価方法
粘着加工した偏光板を25mm×150mmの大きさにカットし、厚さ1.1mmのフロートガラスにラミネータを用いて貼り付け、50℃5気圧の条件のオートクレーブ内に20分保持させてガラス板に密着させた。この試験片を23℃、相対湿度50%で1週間放置した後に、180°ピール試験(剥離速度300mm/min)を実施し、ピール後のガラスの曇りを目視で観察し、二段階で評価した。
◎は「実用上全く問題がない」、△は「実用上問題がある」をそれぞれ意味する。
【0058】
(3)光学特性(ヘイズ)の評価方法
粘着剤を剥離処理されたポリエステルフィルムに塗工して乾燥させ、25μmの粘着剤層を設けた後に、更に剥離処理されたポリエステルフィルムを被せた。この剥離処理ポリエステルフィルムに挟まれた粘着剤層を温度23℃相対湿度50%の条件で1週間熟成させた後、剥離処理ポリエステルフィルムを取り除き、粘着剤層単体のヘイズをNDH−300A(日本電色工業(株)社製)で測定した。
【0059】
【表3】
【0060】
【発明の効果】
本発明の粘着剤を用いることにより、熱あるいは湿熱条件下でも発泡やハガレ等が発生せず、偏光板の伸縮等により生じる応力集中を緩和して液晶素子に色むら・白ぬけを発生させない光学部材を提供できるようになった。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an adhesive used for attaching an optical member such as a polarizing plate or a retardation plate to an optical component such as a liquid crystal cell of a liquid crystal display device, and an optical member using the same.
[0002]
[Prior art]
A polarizing plate or a laminate of a polarizing plate and a retardation plate is attached to an optical component such as a liquid crystal cell of a liquid crystal display device. A polarizing plate generally has a multilayer structure in which both surfaces of a polyvinyl alcohol-based polarizer are sandwiched between triacetyl cellulose-based protective films, and an adhesive is provided on one or both surfaces of the triacetyl cellulose-based protective film. A layer is formed. The polarizing plate is attached to an optical component such as a liquid crystal cell through the adhesive layer and used as a liquid crystal display. 2. Description of the Related Art In recent years, liquid crystal display devices have been widely used in indoor applications such as displays of personal computers and liquid crystal televisions, as well as in on-vehicle applications such as car navigation displays, and their use environments are becoming extremely harsh.
[0003]
Polarizing plates used in liquid crystal display devices have poor dimensional stability due to their material properties, and expand or contract under heat or wet heat conditions, resulting in large changes in dimensions. Problems such as peeling of the polarizing plate from the liquid crystal cell are likely to occur.
As a pressure-sensitive adhesive for solving these problems, there is provided a pressure-sensitive adhesive comprising an acrylic polymer mainly containing an alkyl ester of (meth) acrylic acid having an alkyl group having 1 to 12 carbon atoms, the pressure-sensitive adhesive comprising There is known a pressure-sensitive adhesive comprising an acrylic polymer in which an agent contains 15% by weight or less of a polymer component having a weight average molecular weight of 100,000 or less and 10% by weight or more of a polymer component having a weight average molecular weight of 1,000,000 or more. (For example, refer to Patent Document 1).
[0004]
By using the pressure-sensitive adhesive, foaming of the pressure-sensitive adhesive layer and peeling of the polarizing plate from floating from the liquid crystal cell can be suppressed, but the stress due to the dimensional change of the polarizing plate cannot be absorbed / relaxed, and the polarizing plate cannot be used. Since the stress is concentrated on the peripheral portion, the brightness of the peripheral portion and the central portion of the liquid crystal display device are different from each other, and there has been a problem that color unevenness and whitening occur on the surface of the liquid crystal display device.
As an adhesive for eliminating color unevenness and whitening on the surface of the liquid crystal display device, 100 parts by weight of a high molecular weight (meth) acrylic copolymer having a weight average molecular weight of 1,000,000 or more, and a weight average molecular weight of 30,000 or less are used. 2. Description of the Related Art A pressure-sensitive adhesive for a polarizing plate comprising 20 to 200 parts by weight of a low molecular weight (meth) acrylic copolymer and 0.005 to 5 parts by weight of a polyfunctional compound is known (for example, see Patent Document 2).
[0005]
Further, a high molecular weight acrylic polymer having a weight average molecular weight of 1,000,000 to 2.5 million containing a reactive functional group and a low molecular weight acrylic polymer having a glass transition point of 0 ° C to -80 ° C and a weight average molecular weight of 30,000 to 100,000 2. Description of the Related Art An adhesive composition for a polarizing film comprising a polyfunctional compound having a functional group capable of forming a crosslinked structure is known (for example, see Patent Document 3).
[Patent Document 1]
JP-A-1-66283
[Patent Document 2]
JP-A-10-279907
[Patent Document 3]
JP 2002-121521 A
[0006]
[Problems to be solved by the invention]
Patent Document 2 describes that since the polarizing plate adhesive disclosed in the document can follow the dimensional change of the polarizing plate, color unevenness and white spots hardly occur in the liquid crystal element. However, the polarizing plate pressure-sensitive adhesive disclosed in Patent Document 2 has a low molecular weight (meth) which is hardly crosslinked or does not crosslink in a high molecular weight (meth) acrylic copolymer three-dimensionally crosslinked with a polyfunctional compound. The presence of an acrylic (co) polymer expresses stress relaxation, and can improve color unevenness and white spots, but low molecular weight (meth) acrylic polymers easily bleed and adhere The problem of body contamination remains.
[0007]
Further, Patent Document 3 describes that the pressure-sensitive adhesive composition for a polarizing film disclosed in the document has both a property that color unevenness and whitening hardly occur and a property that a low molecular weight acrylic polymer is hard to bleed. However, in using the liquid crystal display device in a more severe environment, it is difficult to achieve a balance of performance.
Therefore, an object of the present invention is to prevent the pressure-sensitive adhesive layer from foaming or peeling off the polarizing plate even under heat or wet heat conditions, to reduce stress concentration caused by expansion and contraction of the polarizing plate, etc. It is an object of the present invention to provide a pressure-sensitive adhesive that does not cause whitening and that can reduce adherent contamination and haze, which are problems when the polarizing plate is repositioned.
[0008]
[Means for Solving the Problems]
The pressure-sensitive adhesive in the present invention is obtained by radical copolymerization of a high molecular weight copolymer (A), a monomer having a carboxyl group and other monomers in the presence of the copolymer (A). By containing the low molecular weight copolymer (B) and the polyfunctional compound (C) at a specific ratio, a property of alleviating the color unevenness and white drop phenomenon caused by a dimensional change of the polarizing plate; It also has the property of suppressing foaming, peeling and the like even under conditions.
[0009]
That is, the pressure-sensitive adhesive according to the present invention comprises a copolymer (A) having a weight average molecular weight of 1,000,000 to 2,000,000 obtained by radical copolymerization of the following monomers (a) and (b), and the copolymer ( A) A copolymer having a weight average molecular weight of 10,000 or more and 100,000 or less obtained by radically copolymerizing the following monomers (c) and (d) in the presence of the copolymer (A) with respect to 100 parts by weight. 20 to 100 parts by weight of the compound (B), and the polyfunctional compound (C) having at least two reactive functional groups capable of reacting with the copolymer (A) and / or the copolymer (B). It is an adhesive consisting of 003 to 3 parts by weight.
(A) Monomer having reactive functional group and ethylenically unsaturated double bond
(B) Other monomers having an ethylenically unsaturated double bond copolymerizable with (a)
(C) a monomer having a carboxyl group and an ethylenically unsaturated double bond
(D) Another monomer having an ethylenically unsaturated double bond copolymerizable with (c)
In the pressure-sensitive adhesive, the copolymerization ratio of the monomer (a) constituting the copolymer (A) is preferably 0.1 to 15% by weight, and the copolymerization ratio of the monomer (b) is 85%. Preferably, it is 9999.9% by weight.
[0010]
The method for producing a pressure-sensitive adhesive according to the present invention is a method for producing a pressure-sensitive adhesive having the following steps (1) to (3).
(1) a monomer (a) having a reactive functional group and an ethylenically unsaturated double bond and a monomer (b) having another ethylenically unsaturated double bond copolymerizable with (a) A step of polymerizing the copolymer (A) by radical copolymerization at a conversion of 50% to 90%.
(2) Radical copolymerization of a monomer remaining during polymerization of copolymer (A) and monomer (c) having a carboxyl group and an ethylenically unsaturated double bond in the presence of copolymer (A) And polymerizing the copolymer (B).
(3) A step of adding a polyfunctional compound (C) having at least two reactive functional groups capable of reacting with the copolymer (A) and / or the copolymer (B).
[0011]
In the above step (2), the monomer remaining at the time of polymerization of the copolymer (A) and the monomer (c) having a carboxyl group and an ethylenically unsaturated double bond are converted at a conversion rate of 70% to 100%. It is preferable to polymerize the copolymer (B) by radical copolymerization.
The pressure-sensitive adhesive in the present invention is a pressure-sensitive adhesive produced by the above method.
The optical member according to the present invention is an optical member characterized in that an adhesive layer made of any one of the above adhesives is formed on at least one surface of the optical member.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
First, the pressure-sensitive adhesive of the present invention will be described.
The polymer (A) contained in the pressure-sensitive adhesive includes a monomer (a) having a reactive functional group and an ethylenically unsaturated double bond, and another ethylenically unsaturated double bond copolymerizable with (a). It is a copolymer obtained by radical copolymerization of a monomer (b) having a bond. Examples of the reactive functional group include a carboxyl group, a hydroxyl group, an amino group, an amide group, a maleimide group, an itaconimide group, a succinimide group, and an epoxy group. As the monomer (a) and the monomer (b), (meth) acrylic monomers and vinyl monomers are preferably used.
[0013]
Specific examples of the monomer (a) having a carboxyl group include (meth) acrylic acid, β-carboxyethyl acrylate, itaconic acid, crotonic acid, fumaric acid, fumaric anhydride, maleic acid, maleic anhydride, and maleic acid. Butyl and the like. Specific examples of the monomer (a) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylhexyl) -methyl acrylate, chloro-2-hydroxypropyl (meth) acrylate, Examples include diethylene glycol mono (meth) acrylate, caprolactone-modified (meth) acrylates, polyethylene glycol (meth) acrylates, and polypropylene glycol (meth) acrylates.
[0014]
Specific examples of the monomer (a) having an amino group include aminomethyl (meth), dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylate.
Specific examples of the monomer (a) having an amide group include (meth) acrylamide, N-acryloylmorpholine, N-substituted (meth) acrylamide, N-vinylpyrrolidone, and the like.
Specific examples of the monomer (a) having a maleimide group include N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide and the like.
Specific examples of the monomer (a) having an itaconimide group include N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, and N-ethylitaconimide. Cyclohexylitaconimide, N-laurylitaconimide, and the like.
[0015]
Specific examples of the monomer (a) having a succinimide group include N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxy Octamethylene succinimide and the like can be mentioned.
Specific examples of the monomer (a) having an epoxy group include glycidyl (meth) acrylate.
These monomers can be used alone or in combination of two or more.
The copolymerization ratio of the monomer (a) constituting the copolymer (A) is preferably 0.1 to 15% by weight based on the total amount of the monomer. If the copolymerization ratio is less than 0.1% by weight, the cohesive strength of the pressure-sensitive adhesive is reduced, and foaming or floating peeling of the pressure-sensitive adhesive may occur in a heating environment. On the other hand, when the content is more than 15% by weight, it is difficult to exhibit the property of reducing the adhesive strength of the pressure-sensitive adhesive and sufficiently absorbing and relaxing the stress concentration caused by the expansion and contraction of the polarizing plate.
[0016]
Specific examples of the monomer (b) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, Ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, iso-nonyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl ( Examples thereof include (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and phenoxyethyl (meth) acrylate. Further, aromatic vinyl monomers such as styrene, methylstyrene, and vinyltoluene, vinyl acetate, (meth) acrylonitrile, and the like are also included.
[0017]
The copolymerization ratio of the monomer (b) constituting the copolymer (A) is preferably 85 to 99.9% by weight based on the total amount of the monomer. If the copolymerization ratio is less than 85% by weight, the adhesion to a polarizing plate or an optical component decreases. On the other hand, when the content is more than 99.9% by weight, the content of the monomer (a) having a reactive functional group decreases, the cohesive force of the pressure-sensitive adhesive decreases, and the pressure-sensitive adhesive foams and floats under a heating environment. Peeling may occur.
[0018]
The copolymer (A) can be produced by any known method.
For example, the copolymer (A) is prepared by using a polymerization initiator in an amount of 0.001 to 1 part by weight, based on 100 parts by weight of a total of monomers, by a method such as bulk polymerization or solution polymerization, and preferably by a solution weight. Synthesized by law. As the polymerization initiator, an azo compound or an organic peroxide is used, and two or more polymerization initiators may be used in combination. In the case of solution polymerization, as a polymerization solvent, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, methyl ethyl ketone and the like are used. Two or more polymerization solvents may be used in combination.
[0019]
Examples of the azo compound among the polymerization initiators include, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1- (Carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2- Methylpropionate), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazoline) -2-yl) propane].
[0020]
Examples of the organic peroxide include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and di (2-ethoxyethyl). Examples include peroxydicarbonate, t-butylperoxyneodecanoate, t-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like.
[0021]
The weight average molecular weight of the copolymer (A) needs to be 1,000,000 or more and 2,000,000 or less, and more preferably 1.2M or more and 1.8M or less. The copolymer (A) having a weight-average molecular weight of less than 1,000,000 is insufficient in cohesive force of the pressure-sensitive adhesive even when used in a crosslinked state, and causes foaming and floating peeling. On the other hand, when the weight average molecular weight is more than 2,000,000, the viscosity of the pressure-sensitive adhesive becomes high, and the workability such as coating is poor. The weight average molecular weight of the copolymer (A) is determined by sampling a part of the reaction solution before starting the polymerization of the copolymer (B) and performing gel permeation chromatography (GPC) measurement. calculate.
[0022]
The copolymer (B) contained in the pressure-sensitive adhesive can be copolymerized with the monomers (c) and (c) having a carboxyl group and an ethylenically unsaturated double bond in the presence of the copolymer (A). It is a copolymer having a weight average molecular weight of 10,000 or more and 100,000 or less obtained by radically copolymerizing another monomer (d) having an ethylenically unsaturated double bond. The copolymer (B) having a lower molecular weight than the copolymer (A) obtained by radical copolymerization of the monomer (c) and the monomer (d) in the presence of the copolymer (A) is used as an adhesive. When it is contained therein, foaming or peeling of the pressure-sensitive adhesive does not occur even under heat or moist heat conditions, stress concentration caused by expansion and contraction of the polarizing plate is relieved, and color unevenness and whitening phenomenon do not occur in the liquid crystal element.
[0023]
As the monomer (c) and the monomer (d), (meth) acrylic monomers and vinyl monomers are suitably used. Specific examples of the monomer (c) include (meth) acrylic acid, β-carboxyethyl acrylate, itaconic acid, crotonic acid, fumaric acid, fumaric anhydride, maleic acid, maleic anhydride, butyl maleate and the like. Can be These monomers can be used alone or in combination of two or more.
The copolymerization ratio of the monomer (c) constituting the copolymer (B) is 0.1 to 50% by weight based on the total amount of the monomer (c) and the monomer (d). And more preferably 0.5 to 30% by weight.
[0024]
As the monomer (d), among the monomers (a) constituting the copolymer (A), a monomer (a) having a reactive functional group other than a carboxyl group and a monomer (b) ) Can be used.
The copolymer (B) is, in the presence of the copolymer (A), a monomer having a carboxyl group and an ethylenically unsaturated double bond (c) and another ethylenic copolymerizable with (c). The monomer (d) having an unsaturated double bond can be produced by radical copolymerization in the same manner as in the copolymer (A). The copolymer (B) is obtained by radically copolymerizing the monomer (a) and the monomer (b) at a conversion of 50 to 90% to polymerize the copolymer (A), and the remaining monomer And the monomer (c) are preferably produced by radical copolymerization in the presence of the copolymer (A).
[0025]
Further, it is preferable that the monomer remaining during the polymerization of the copolymer (A) and the monomer (c) undergo radical copolymerization at a conversion of 70 to 100%. Here, the conversion is a value obtained by dividing the weight of the copolymer obtained by polymerizing the monomer by the total weight of the monomer used as a raw material.
By polymerizing the copolymer (A) and the copolymer (B) at the above conversion, the copolymer (B) is in a range of 20 to 100 parts by weight based on 100 parts by weight of the copolymer (A). It becomes easy to fit in.
[0026]
It is preferable that the copolymer (B) is synthesized by a solution polymerization method. It is preferable to use 0.005 to 50 parts by weight of a polymerization initiator. When synthesizing the copolymer (B), mercaptans such as lauryl mercaptan and n-dodecyl mercaptan, and chain transfer agents such as α-methylstyrene dimer and limonene may be used.
[0027]
The weight average molecular weight of the copolymer (B) needs to be 10,000 or more and 100,000 or less, and more preferably 20,000 or more and 50,000 or less. When a copolymer (B) having a weight average molecular weight of less than 10,000 is used, the cohesive force is insufficient and foaming and floating peeling are likely to occur. When a copolymer (B) having a weight average molecular weight of more than 100,000 is used, a property of sufficiently absorbing and relaxing stress concentration caused by expansion and contraction of the polarizing plate is hardly exhibited. Here, the weight average molecular weight of the copolymer (B) is determined by measuring the mixture of the copolymer (A) and the copolymer (B) by GPC, and obtaining the obtained GPC spectrum and the copolymer ( It is calculated from the difference spectrum from the GPC spectrum of A).
[0028]
The content of the copolymer (B) contained in the pressure-sensitive adhesive is 20 to 100 parts by weight, preferably 20 to 50 parts by weight, based on 100 parts by weight of the copolymer (A). When the content of the copolymer (B) is less than 20 parts by weight, the property of sufficiently absorbing and relaxing the stress concentration caused by the expansion and contraction of the polarizing plate is hardly exhibited. When the content of the copolymer (B) is more than 100 parts by weight, the cohesive force of the pressure-sensitive adhesive is insufficient, and foaming and floating peeling are likely to occur.
[0029]
The weight ratio of the copolymer (A) to the copolymer (B) is determined by the following method. That is, first, a certain amount of the solution sampled before the polymerization of the polymer (B) is started is precisely weighed in a container having a known weight, and the precisely weighed solution is heated and dried to obtain a solution other than the copolymer. The components are volatilized, the container in which only the copolymer (A) remains is precisely weighed, and the weight of the copolymer (A) contained in a certain amount of the solution is calculated. Next, after the polymerization of the copolymer (B) is completed, a solution containing the copolymer (A) and the copolymer (B) is sampled, and a method similar to that used when the weight of the copolymer (A) is calculated. Then, the weights of the copolymer (A) and the copolymer (B) contained in a certain amount of the solution are calculated. Then, the weight of the copolymer (A) and the mixture of the copolymer (A) and the copolymer (B) contained in the fixed amount of the solution is reduced by the weight of the copolymer (A) and the copolymer The weight of the mixture of the copolymer (A) and the copolymer (B) is converted to the weight of the mixture, and the copolymer (A) is subtracted from the weight of the mixture of the copolymer (A) and the copolymer (B) to obtain a copolymer. The weight of the combination (B) is calculated.
[0030]
The copolymer (A) has a copolymer (A) having at least two reactive functional groups capable of reacting with the copolymer (A) and / or the copolymer (B) contained in the pressure-sensitive adhesive. It is a compound having at least two, preferably 2 to 4 reactive functional groups capable of reacting with a reactive functional group and / or a carboxyl group contained in the copolymer (B) or a reactive functional group other than the carboxyl group. Examples of such a polyfunctional compound include an isocyanate compound, an epoxy compound, an amine compound, a metal chelate compound, and an aziridine compound. In particular, isocyanate compounds, epoxy compounds, and aziridine compounds are preferred. The polyfunctional compounds can be used alone or in combination.
[0031]
Examples of isocyanate compounds include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethyl xylylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate. Isocyanates, polyisocyanate compounds such as polymethylene polyphenylisocyanate, and adducts of these polyisocyanate compounds and polyol compounds such as trimethylolpropane, burettes and isocyanurates of these polyisocyanate compounds, and furthermore, these polyisocyanate compounds Known polyether polyols and polyethers Ether polyols, acrylic polyols, polybutadiene polyols, adducts, etc. and polyisoprene polyol and the like.
[0032]
Examples of the epoxy compound include bisphenol A-epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, and 1,6-hexane. Diol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N'-diglycidylaminomethyl ) Cyclohexane, N, N, N ', N'-tetraglycidylaminophenylmethane, triglycidyl and the like.
[0033]
Examples of the aziridine compound include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis (1-aziridinecarboxite), Bisisophthaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N'-hexamethylene-1,6-bis (1-aziridinecarboxite), trimethylolpropanetri- β-aziridinylpropionate, tetramethylolmethanetri-β-aziridinylpropionate, tris-2,4,6- (1-aziridinyl) -1,3,5-triazine and the like.
[0034]
The content of the polyfunctional compound (C) is 0.003 to 3 parts by weight based on 100 parts by weight of the copolymer (A). If the content of the polyfunctional compound (C) is less than 0.003 parts by weight, the cohesive force of the colorant is insufficient, and foaming and floating peeling are likely to occur. When the amount is more than 3 parts by weight, the property of sufficiently absorbing and relaxing the stress concentration caused by the expansion and contraction of the polarizing plate is hardly exhibited.
[0035]
It is preferable to mix a silane coupling agent with the adhesive. Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyl Dimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyl Methoxysilane N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-merca DOO triethoxysilane, mercaptopropyl butyl trimethoxysilane γ- mercaptopropyl methyl dimethoxy silane, and the like.
[0036]
The content of the silane coupling agent in the adhesive is preferably 0.01 to 2 parts by weight based on 100 parts by weight of the copolymer (A). If the amount is less than 0.01 part by weight, the effect of improving the physical properties is poor, and if it exceeds 2 parts by weight, the pressure-sensitive adhesive becomes not only expensive but also causes floating peeling.
Further, an ultraviolet absorber, an antioxidant, a tackifier resin, a plasticizer, an antifoaming agent, and a leveling regulator may be added to the adhesive.
[0037]
The pressure-sensitive adhesive can be manufactured through the following steps (1) to (3).
(1) a monomer (a) having a reactive functional group and an ethylenically unsaturated double bond and a monomer (b) having another ethylenically unsaturated double bond copolymerizable with (a) A step of polymerizing the copolymer (A) by radical copolymerization at a conversion of 50 to 90%.
(2) A monomer remaining at the time of polymerization of the copolymer (A) and a monomer (c) having a carboxyl group and an ethylenically unsaturated double bond are converted at a conversion rate of 70 in the presence of the copolymer (A). A step of polymerizing the copolymer (B) by radical copolymerization at a concentration of 100% to 100%.
(3) A step of adding a polyfunctional compound (C) having at least two reactive functional groups capable of reacting with the copolymer (A) and / or the copolymer (B).
[0038]
Next, the optical member of the present invention will be described.
The optical member of the present invention is an optical member in which an adhesive layer made of the adhesive of the present invention is formed on at least one surface of the optical member.
Examples of the optical member forming the pressure-sensitive adhesive layer include a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film.
[0039]
The formation of the pressure-sensitive adhesive layer can be performed using a commonly used coating apparatus. Examples of the coating device include a roll knife coater, a die coater, a roll coater, a bar coater, a gravure roll coater, a reverse roll coater, a dipping, and a blade coater.
The dry thickness of the pressure-sensitive adhesive layer is preferably 5 to 100 μm in consideration of an appropriate thickness and economy for absorbing and relaxing stress concentration caused by expansion and contraction of the polarizing plate.
[0040]
【Example】
Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In the following description, parts and% mean parts by weight and% by weight, respectively.
(Synthesis example 1)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen inlet tube, 99.0 parts of n-butyl acrylate, 1.0 part of 4-hydroxybutyl acrylate, 150.0 parts of acetone, 2,2 After charging 0.06 parts of '-azobisisobutyronitrile and replacing the air in the reaction vessel with nitrogen gas, the reaction solution was heated to 60 ° C under a nitrogen atmosphere while stirring, and Allowed to react for hours. After the completion of the reaction, 190 parts of toluene, 0.25 part of acrylic acid and 0.50 part of 2,2'-azobis (2,4-dimethylvaleronitrile) were added, and the temperature was raised to 70 ° C and the reaction was carried out for 6 hours. I let it. After the reaction, 55 parts of toluene was added and the mixture was cooled to room temperature to obtain a polymer solution A having a solid content of 20.0%.
[0041]
(Synthesis examples 2 to 9)
As shown in Table 1, a monomer (a) having a reactive functional group and an ethylenically unsaturated double bond, and a monomer having another ethylenically unsaturated double bond copolymerizable with (a) Polymer solutions B to I were obtained in the same manner as in Synthesis Example 1 except that the type and amount of (b), the monomer (c) having a carboxyl group and an ethylenically unsaturated double bond were changed.
[0042]
(Synthesis example 10)
In a reaction apparatus similar to that of Synthesis Example 1, 99.0 parts of butyl acrylate, 1.0 part of 4-hydroxybutyl acrylate, 163.0 parts of ethyl acetate, and 0.06 part of 2,2′-azobisisobutyronitrile were added. After charging and replacing the air in the reaction vessel with nitrogen gas, the reaction solution was heated to 80 ° C. in a nitrogen atmosphere with stirring and reacted for 4 hours. After completion of the reaction, 176 parts of toluene, 0.25 part of acrylic acid and 0.50 part of 2,2′-azobis (2,4-dimethylvaleronitrile) were added, the temperature was raised to 75 ° C., and the reaction was performed for 6 hours. I let it. After the reaction, 57 parts of toluene was added and the mixture was cooled to room temperature to obtain a polymer solution J having a solid content of 20.0%.
[0043]
(Synthesis Example 11)
In the same reactor as in Synthesis Example 1, 60.0 parts of butyl acrylate, 37.0 parts of 2-ethylhexyl acrylate, 3.0 parts of 4-hydroxybutyl acrylate, 150.0 parts of acetone, 2,2′-azobisiso After charging 0.06 parts of butyronitrile and replacing the air in the reaction vessel with nitrogen gas, the reaction solution was heated to 60 ° C. in a nitrogen atmosphere with stirring and reacted for 5 hours. After completion of the reaction, 65.0 parts of ethyl acetate, 0.28 part of acrylic acid and 0.06 part of 2,2′-azobisisobutyronitrile were added, the temperature was raised to 60 ° C., and the reaction was carried out for 8 hours. Was. After the reaction, 183 parts of toluene was added and the mixture was cooled to room temperature to obtain a polymer solution K having a solid content of 20.0%.
[0044]
(Synthesis Example 12)
The same reactor as in Synthesis Example 1 was charged with 99.0 parts of butyl acrylate, 1.0 part of 4-hydroxybutyl acrylate, 150.0 parts of acetone, and 0.06 part of 2,2′-azobisisobutyronitrile. After replacing the air in the reaction vessel with nitrogen gas, the reaction solution was heated to 60 ° C. in a nitrogen atmosphere with stirring, and reacted for 3 hours. After completion of the reaction, 1.1 parts of toluene, 0.55 part of acrylic acid and 1.1 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) were added, and the temperature was raised to 70 ° C. Allowed to react for hours. After the reaction, 236 parts of toluene was added and the mixture was cooled to room temperature to obtain a polymer solution L having a solid content of 20.0%.
[0045]
(Synthesis Example 13)
The same reactor as in Synthesis Example 1 was charged with 99.0 parts of butyl acrylate, 1.0 part of 4-hydroxybutyl acrylate, 150.0 parts of acetone, and 0.06 part of 2,2′-azobisisobutyronitrile. After replacing the air in the reaction vessel with nitrogen gas, the reaction solution was heated to 60 ° C. in a nitrogen atmosphere with stirring, and reacted for 10 hours. After completion of the reaction, 198 parts of toluene, 0.08 part of acrylic acid and 0.16 part of 2,2′-azobis (2,4-dimethylvaleronitrile) were added, and the temperature was raised to 70 ° C., and the reaction was performed for 6 hours. I let it. After the reaction, 51 parts of toluene was added and the mixture was cooled to room temperature to obtain a polymer solution M having a solid content of 20.0%.
[0046]
(Synthesis Example 14)
In a reaction vessel similar to that of Synthesis Example 1, 99.0 parts of n-butyl acrylate, 1.0 part of 4-hydroxybutyl acrylate, 150.0 parts of acetone, 0.06 parts of 2,2′-azobisisobutyronitrile After the air in the reaction vessel was replaced with nitrogen gas, the reaction solution was heated to 60 ° C. in a nitrogen atmosphere with stirring and reacted for 5 hours. After the reaction, 150 parts of toluene was added and the mixture was cooled to room temperature to obtain a polymer solution N having a solid content of 20.0%. The weight average molecular weight of the polymer was 16.1 million, and Mw / Mn was 4.8.
[0047]
(Synthesis Example 15)
In a reaction vessel similar to that of Synthesis Example 1, 99.0 parts of n-butyl acrylate, 1.0 part of 4-hydroxybutyl acrylate, 150.0 parts of toluene, 1 part of α-methylstyrene dimer and 2,2′-azobis After charging 2 parts of isobutyronitrile and replacing the air in the reaction vessel with nitrogen gas, the reaction solution was heated to 70 ° C. under a nitrogen atmosphere with stirring, and reacted for 6 hours. After the reaction, 150 parts of toluene was added and the mixture was cooled to room temperature to obtain a polymer solution O having a solid content of 40.0%. The weight average molecular weight of the polymer was 24,000, and Mw / Mn was 2.8.
[0048]
For the polymer solutions obtained in Synthesis Examples 1 to 13, the weight average molecular weight (Mw) of the copolymer (A), the conversion during the synthesis of the copolymer (A), and the weight average molecular weight of the copolymer (B) (Mw), the conversion during the synthesis of the copolymer (B), and the ratio of the copolymer (B) to 100 parts of the copolymer (A) were calculated by the methods described above. Table 1 shows the results.
[0049]
[Table 1]
[0050]
The abbreviations of the monomers in Table 1 are shown below.
4-HBA: 4-hydroxybutyl acrylate
AA: Acrylic acid
HEA: 2-hydroxyethyl acrylate
HEMA: 2-hydroxyethyl methacrylate
BA: butyl acrylate
2EHA: 2-ethylhexyl acrylate
LA: lauryl acrylate
EA: ethyl acrylate
VAc: vinyl acetate
[0051]
The weight average molecular weight of the copolymer is a polystyrene equivalent weight average molecular weight determined by GPC measurement, and the GPC measurement conditions are as follows.
Apparatus: Shodex GPC System-21 (manufactured by Showa Denko KK)
Column: A total of three Shodex KF-602.5 and two Shodex KF-606M (manufactured by Showa Denko KK) are connected and used.
Solvent: tetrahydrofuran
Flow rate: 0.5 ml / min
Temperature: 40 ° C
Sample concentration: 0.1 wt%
Sample injection volume: 50 μl
[0052]
(Example 1)
Based on 100 parts by weight of the polymer solution A obtained in Synthesis Example 1, 0.05 parts of XDI / TMP (trimethylopropane adduct of xylylene diisocyanate) and a silane coupling agent (Shin-Etsu Chemical Co., Ltd.) ) Manufactured by “KBM403”) was added and stirred well to obtain an adhesive. This pressure-sensitive adhesive was applied to a peeled polyester film and dried. After a pressure-sensitive adhesive layer having a thickness of 25 μm was provided, the pressure-sensitive adhesive layer was transferred to one surface of the polarizing film, and the polarizing film was subjected to pressure-sensitive adhesive processing. The adhesive-processed polarizing film was aged for one week at a temperature of 23 ° C. and a relative humidity of 50% to obtain a polarizing plate.
[0053]
(Examples 2 to 7 and Comparative Examples 1 to 7)
An adhesive was produced in exactly the same manner as in Example 1 except that the types and amounts of the polymer solution, the polyfunctional compound (C), and the silane coupling agent shown in Table 2 were used, and the obtained adhesive was used. Was used to prepare a polarizing plate subjected to adhesive processing.
(Comparative Example 8)
A pressure-sensitive adhesive was produced in exactly the same manner as in Example 1, except that a polymer solution obtained by mixing 100 parts of the polymer solution N and 30 parts of the polymer solution O was used instead of the polymer solution A. Using the obtained adhesive, a polarizing plate which was subjected to adhesive processing was prepared.
[0054]
[Table 2]
[0055]
Abbreviations of the polyfunctional compound and the silane coupling agent in Table 2 are shown below.
TAT: Tris-2,4,6- (1-aziridinyl) -1,3,5-triazine TGMXDA: N, N, N ′, N′-tetraglycidyl-m-xylylenediamine
KBM903: Shin-Etsu Chemical Co., Ltd. silane coupling agent “KBM903”
KBM803: Silane coupling agent “KBM803” manufactured by Shin-Etsu Chemical Co., Ltd.
KBM9007: Silane coupling agent “KBM9007” manufactured by Shin-Etsu Chemical Co., Ltd.
[0056]
With respect to the pressure-sensitive adhesives obtained in Examples and Comparative Examples, and the polarizing plate subjected to pressure-sensitive adhesive processing, the heat resistance performance, the moist heat resistance performance, the optical characteristics, and the reworkability were evaluated by the following methods. Table 3 shows the results.
(1) Evaluation method of heat resistance performance, wet heat resistance performance, and optical characteristics (white)
The adhesive-processed polarizing plate was cut into a size of 150 mm × 80 mm, and attached to both sides of a float glass plate having a thickness of 1.1 mm using a laminator such that the absorption axes of the polarizing plate were orthogonal to each other. Subsequently, the glass plate to which the polarizing plate was attached was held in an autoclave at 50 ° C. and 5 atm for 20 minutes to adhere to the glass plate. Furthermore, the peeling of the components of the polarizing plate and the glass plate after leaving at 80 ° C. for 500 hours (heat resistance), the lifting of after leaving the components at 60 ° C. and a relative humidity of 90% for 500 hours (moisture and heat resistance), and After leaving at 60 ° C. and a relative humidity of 90% for 500 hours, light leakage (white spots) when light was transmitted through the components of the polarizing plate and the glass plate was visually observed and evaluated in three steps.
◎ indicates `` floating peeling / blanket is not recognized at all '', ○ indicates `` slight floating peeling / blanket is recognized, but there is no practical problem '', △ indicates `` clear floating peeling / blanket is recognized, There is a practical problem. "
[0057]
(2) Reworkability evaluation method
The adhesive-processed polarizing plate is cut into a size of 25 mm × 150 mm, and is attached to a 1.1 mm-thick float glass using a laminator, and held in an autoclave at 50 ° C. and 5 atm for 20 minutes to form a glass plate. Closely attached. After leaving this test piece at 23 ° C. and a relative humidity of 50% for one week, a 180 ° peel test (peeling rate: 300 mm / min) was performed, and clouding of the glass after peeling was visually observed and evaluated in two steps. .
◎ means “there is no practical problem”, and △ means “there is a practical problem”.
[0058]
(3) Evaluation method of optical characteristics (haze)
The pressure-sensitive adhesive was applied to the release-treated polyester film and dried. After providing a 25-μm pressure-sensitive adhesive layer, the release-treated polyester film was further covered. After the pressure-sensitive adhesive layer sandwiched between the release-treated polyester films was aged for one week at a temperature of 23 ° C. and a relative humidity of 50%, the release-treated polyester film was removed, and the haze of the pressure-sensitive adhesive layer alone was reduced to NDH-300A (Nippon Denki). Color Industry Co., Ltd.).
[0059]
[Table 3]
[0060]
【The invention's effect】
By using the pressure-sensitive adhesive of the present invention, foaming or peeling does not occur even under heat or wet heat conditions, stress concentration caused by expansion and contraction of a polarizing plate and the like is relaxed, and optical unevenness and whitening are not generated in a liquid crystal element. A member can now be provided.
Claims (6)
(a) 反応性官能基およびエチレン性不飽和二重結合を有する単量体
(b) (a)と共重合可能な他のエチレン性不飽和二重結合を有する単量体
(c) カルボキシル基およびエチレン性不飽和二重結合を有する単量体
(d)(c)と共重合可能な他のエチレン性不飽和二重結合を有する単量体With respect to a copolymer (A) having a weight average molecular weight of 1,000,000 to 2,000,000 obtained by radical copolymerization of the following monomers (a) and (b), and 100 parts by weight of the copolymer (A), 20 to 100 parts by weight of a copolymer (B) having a weight average molecular weight of 10,000 to 100,000 obtained by radical copolymerization of the following monomers (c) and (d) in the presence of the copolymer (A) And a pressure-sensitive adhesive comprising 0.003 to 3 parts by weight of a polyfunctional compound (C) having at least two reactive functional groups capable of reacting with the copolymer (A) and / or the copolymer (B). .
(A) a monomer having a reactive functional group and an ethylenically unsaturated double bond (b) a monomer having another ethylenically unsaturated double bond copolymerizable with (a) (c) a carboxyl group And other monomers having an ethylenically unsaturated double bond copolymerizable with monomers (d) and (c) having an ethylenically unsaturated double bond
(1)反応性官能基およびエチレン性不飽和二重結合を有する単量体(a)および(a)と共重合可能な他のエチレン性不飽和二重結合を有する単量体(b)を転化率50〜90%でラジカル共重合して共重合体(A)を重合する工程。
(2)共重合体(A)の重合時に残留する単量体とカルボキシル基およびエチレン性不飽和二重結合を有する単量体(c)を共重合体(A)の存在下でラジカル共重合して共重合体(B)を重合する工程。
(3)共重合体(A)および/または共重合体(B)と反応可能な反応性官能基を少なくとも2個有する多官能性化合物(C)を添加する工程。A method for producing a pressure-sensitive adhesive, comprising the following steps (1) to (3).
(1) a monomer (a) having a reactive functional group and an ethylenically unsaturated double bond and a monomer (b) having another ethylenically unsaturated double bond copolymerizable with (a) A step of polymerizing the copolymer (A) by radical copolymerization at a conversion of 50 to 90%.
(2) Radical copolymerization of a monomer remaining during polymerization of copolymer (A) and monomer (c) having a carboxyl group and an ethylenically unsaturated double bond in the presence of copolymer (A) And polymerizing the copolymer (B).
(3) A step of adding a polyfunctional compound (C) having at least two reactive functional groups capable of reacting with the copolymer (A) and / or the copolymer (B).
Priority Applications (4)
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JP2003125145A JP4534431B2 (en) | 2003-04-30 | 2003-04-30 | Adhesive and optical member using the same |
TW093110078A TWI301147B (en) | 2003-04-30 | 2004-04-12 | Adhesive agent, and an optical part using the same |
KR1020040028901A KR100737653B1 (en) | 2003-04-30 | 2004-04-27 | Adhesive agent, and an optical part using the same |
CNB2004100385528A CN100523109C (en) | 2003-04-30 | 2004-04-30 | Adhesive and optical parts using the same |
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JPH111670A (en) * | 1997-06-13 | 1999-01-06 | Nippon Shokubai Co Ltd | Pressure-sensitive adhesive article |
JP2000080211A (en) * | 1998-07-01 | 2000-03-21 | Mitsui Chemicals Inc | Aqueous dispersion composition and its production |
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JP2000109771A (en) * | 1998-10-07 | 2000-04-18 | Lintec Corp | Adhesive sheet |
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JP3827364B2 (en) * | 1995-06-16 | 2006-09-27 | 日本化薬株式会社 | Adhesive |
JP4673957B2 (en) | 2000-05-30 | 2011-04-20 | リンテック株式会社 | Adhesive composition, adhesive sheet using the same, and adhesive optical member |
KR100405309B1 (en) * | 2000-12-13 | 2003-11-12 | 주식회사 엘지화학 | Acrylic pressure sensitive adhesive for the polarizing firm |
JP2003049141A (en) | 2001-08-03 | 2003-02-21 | Saiden Chemical Industry Co Ltd | Adhesive composition for polarizing plate |
JP4062668B2 (en) | 2002-05-15 | 2008-03-19 | 日東電工株式会社 | Adhesive optical film, optical film adhesive composition and image display device |
KR100668943B1 (en) * | 2004-04-23 | 2007-01-12 | 주식회사 엘지화학 | Acrylic Pressure-Sensitive Adhesive Composition for the Polarizing Film |
-
2003
- 2003-04-30 JP JP2003125145A patent/JP4534431B2/en not_active Expired - Lifetime
-
2004
- 2004-04-12 TW TW093110078A patent/TWI301147B/en not_active IP Right Cessation
- 2004-04-27 KR KR1020040028901A patent/KR100737653B1/en active IP Right Grant
- 2004-04-30 CN CNB2004100385528A patent/CN100523109C/en not_active Expired - Lifetime
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JPS61264077A (en) * | 1985-05-17 | 1986-11-21 | Nitto Electric Ind Co Ltd | Water-dispersed type pressure-sensitive adhesive composition |
JPH10279907A (en) * | 1997-04-09 | 1998-10-20 | Soken Chem & Eng Co Ltd | Pressure sensitive adhesive composition for polarizing plate and polarizing plate |
JPH111670A (en) * | 1997-06-13 | 1999-01-06 | Nippon Shokubai Co Ltd | Pressure-sensitive adhesive article |
JP2000080211A (en) * | 1998-07-01 | 2000-03-21 | Mitsui Chemicals Inc | Aqueous dispersion composition and its production |
JP2000080212A (en) * | 1998-07-01 | 2000-03-21 | Mitsui Chemicals Inc | Aqueous dispersion and its production |
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JP2002121521A (en) * | 2000-10-13 | 2002-04-26 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive composition for polarizing film and polarizing film |
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JP2007031506A (en) * | 2005-07-25 | 2007-02-08 | Nitto Denko Corp | Adhesive composition for optical member, adhesive layer for optical member, method for manufacturing the same, adhesive optical member and image display device |
JP2008044984A (en) * | 2006-08-11 | 2008-02-28 | Toyo Ink Mfg Co Ltd | Pressure-sensitive adhesive composition and pressure-sensitive adhesive film using the same pressure-sensitive adhesive composition |
JP2008291071A (en) * | 2007-05-23 | 2008-12-04 | Toyo Ink Mfg Co Ltd | Pressure-sensitive adhesive composition and stacked body |
US8139039B2 (en) | 2007-07-31 | 2012-03-20 | Kent Displays, Incorporated | Selectively erasable electronic writing tablet |
US8228301B2 (en) | 2007-07-31 | 2012-07-24 | Kent Displays Incorporated | Multiple color writing tablet |
JP2009173721A (en) * | 2008-01-23 | 2009-08-06 | Toyo Ink Mfg Co Ltd | Antistatic acrylic pressure-sensitive adhesive and antistatic pressure-sensitive adhesive film using the same |
JP2010159346A (en) * | 2009-01-08 | 2010-07-22 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive agent and optical film |
JP2012126757A (en) * | 2010-12-13 | 2012-07-05 | Toyo Ink Sc Holdings Co Ltd | Pressure-sensitive adhesive and laminate using the same |
US9134561B2 (en) | 2011-11-01 | 2015-09-15 | Kent Displays Incorporated | Writing tablet information recording device |
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JP2013181086A (en) * | 2012-03-01 | 2013-09-12 | Sumitomo Chemical Co Ltd | Adhesive composition, adhesive sheet, optical film with adhesive and optical laminate |
JP2013189601A (en) * | 2012-03-15 | 2013-09-26 | Toyo Ink Sc Holdings Co Ltd | Adhesive and adhesive film using the same |
US9116379B2 (en) | 2012-05-22 | 2015-08-25 | Kent Displays Incorporated | Electronic display with semitransparent back layer |
US9235075B2 (en) | 2012-05-22 | 2016-01-12 | Kent Displays Incorporated | Electronic display with patterned layer |
US9946106B2 (en) | 2012-05-22 | 2018-04-17 | Kent Displays Inc. | Electronic display with semitransparent back layer |
JP2014074122A (en) * | 2012-10-04 | 2014-04-24 | Nippon Carbide Ind Co Inc | Adhesive composition, adhesive sheet and optical laminated sheet |
US10088701B2 (en) | 2013-11-01 | 2018-10-02 | Kent Displays Inc. | Electronic writing device with dot pattern recognition system |
US9851612B2 (en) | 2014-04-02 | 2017-12-26 | Kent Displays Inc. | Liquid crystal display with identifiers |
JP2017145279A (en) * | 2016-02-15 | 2017-08-24 | サイデン化学株式会社 | Adhesive composition for polarizing plate |
JP2018159019A (en) * | 2017-03-23 | 2018-10-11 | 綜研化学株式会社 | Adhesive sheet |
Also Published As
Publication number | Publication date |
---|---|
CN1570007A (en) | 2005-01-26 |
CN100523109C (en) | 2009-08-05 |
KR100737653B1 (en) | 2007-07-09 |
KR20040094325A (en) | 2004-11-09 |
TWI301147B (en) | 2008-09-21 |
JP4534431B2 (en) | 2010-09-01 |
TW200427804A (en) | 2004-12-16 |
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